25856-00-2

Upstream product

• 10259-22-0 ethyl 3-methoxybenzoate 
• 98-86-2 acetophenone 
• 93-89-0 benzoic acid ethyl ester 
• 586-37-8 1-(3-Methoxyphenyl)ethanone 
• 93-58-3 benzoic acid methyl ester 
• 15206-55-0 methyl 2-oxo-2-phenylacetate 
• 5000-65-7 2-bromo-3'-methoxyacetophenone 
• 98-88-4 benzoyl chloride 
• 24475-94-3 1-(3-methoxyphenyl)-3-phenylprop-2-yn-1-one 
• 932-90-1 Benzaldoxime 

Downstream Products

• 586-38-9 3-Methoxybenzoic acid 
• 65-85-0 benzoic acid 
• 1011508-03-4 C₂₃H₂₄O₃ 
• 1045345-90-1 2-[1-(4-methoxyphenyl)-3-phenyl-2-propynyl]-1-(3-methoxyphenyl)-3-phenyl-1,3-propanedione 
• 1160617-04-8 C₂₄H₂₄N₆O₃ 
• 1160617-00-4 C₂₅H₂₆N₆O₂ 
• 1160617-06-0 C₂₇H₂₉N₇O₃ 
• 40103-80-8 1-(3-methoxyphenyl)-2-phenylethane-1,2-dione 

Relevant academic research and scientific papers

2-Hydroxylation of 1,3-Diketones with Atmospheric Oxygen

An efficient method for the 2-hydroxylation of 1,3-diketones by using atmospheric oxygen as an oxidant under transition-metal-free condition is described. The protocol has the advantages of using an inexpensive and stable oxidant, producing high yields, and requiring ecofriendly conditions.

Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils

The conversion of 1,3-diaryl-2-diazo-1,3-diketones to 1,2-daryl-1,2-diketones (benzils) is reported based on a rhodium(II)-catalyzed aerobic decomposition process. The reaction occurs at ambient temperatures and can be catalyzed by a few dirhodium carboxylates (5 mol %) under a balloon pressure of oxygen. Moreover, an oxygen atom from the O2 reagent is shown to be incorporated into the product, and this is accompanied by the extrusion of a carbonyl unit from the starting materials. Mechanistically, it is proposed that the decomposition may proceed via the interaction of a ketene intermediate resulting from a Wolff rearrangement of the carbenoid, with a rhodium peroxide or peroxy radical species generated upon the activation of molecular oxygen. The proposed mechanism has been supported by the results from a set of controlled experiments. By using this newly developed strategy, a large array of benzil derivatives as well as 9,10-phenanthrenequinone were synthesized from the corresponding diazo substrates in varying yields. On the other hand, the method did not allow the generation of benzocyclobutene-1,2-dione from 2-diazo-1,3-indandione because of the difficulty of inducing the initial rearrangement.

An effective preparation of both 1,3-diketones and nitriles from alkynones with oximes as hydroxide sources

An effective phosphine-catalyzed protocol has been established for the syntheses of 1,3-diketones and nitriles from alkynones with oximes as hydroxide surrogates. This method features the use of a phosphine catalyst, compatibility with various functional groups and ambient temperature, which makes this approach very practical. A plausible mechanism was proposed.

Room-Temperature Coupling/Decarboxylation Reaction of α-Oxocarboxylates with α-Bromoketones: Solvent-Controlled Regioselectivity for 1,2- and 1,3-Diketones

A transition-metal-free and room-temperature coupling/decarboxylation reaction between α-oxocarboxylates and α-bromoketones is reported herein. It represents the first mild and regioselective synthesis of either 1,2- or 1,3-diketones from the same starting materials. Notably, the regioselectivity is simply controlled by solvents. The preliminary experimental data and DFT calculations suggest sequential Darzens-type coupling, alkaline hydrolysis, KOH-promoted oxirane opening and decarboxylation in one pot. This method is efficient for the synthesis of α,β-epoxy-γ-butyrolactone and curcuminoids.

Transition-metal-free formal decarboxylative coupling of ?±-oxocarboxylates with ?±-bromoketones under neutral conditions: A simple access to 1,3-diketones

A transition-metal-free formal decarboxylative coupling reaction between ?±-oxocarboxylates and ?±-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the ?±-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.

Asymmetric transfer hydrogenation of unsymmetrical benzils

In this paper, the asymmetric transfer hydrogenation of unsymmetrical benzils with m, p-substituents was conducted with a substrate/catalyst molar ratio of 100 at 40°C for 24 h to produce (S,S)-hydrobenzoins in good yields (76.2% to 97.1%) with high diastereomeric (syn/anti = 10.8 to 29.7/1) and enantiomeric purities (86.1%ee syn to 98.9%ee syn). Unfortunately, the unsymmetrical benzils with the o-substituents such as electron-donating (R = CH3, OCH3) and electron-withdrawing groups (R = F, Cl, CF3) resulted in poor yields (0% to 31.2%), even at 40°C for 72 h. These products had inefficient diastereoselectivities (syn/anti = 1.5 to 5.0/1) caused by steric effects. Furthermore, the results of a dynamic-kinetic study were used to propose a plausible reaction pathway of unsymmetrical benzil using 3-methoxy-1,2-diphenyl ethanedione as an example.